Compounds and Organic Electronic Devices

ABSTRACT

The present invention relates to certain fluorenes, to the use of the compounds in an electronic device, and to an electronic device comprising at least one of these compounds. The present invention furthermore relates to a process for the preparation of the compounds and to a formulation and composition comprising one or more of the compounds.

The present invention relates to novel organic compounds, to the use ofthe compounds in an electroluminescent device, and to anelectroluminescent device comprising at least one of the compounds. Thepresent invention furthermore relates to a process for the preparationof the compounds and to compositions and formulations comprising atleast one of the compounds.

The development of functional compounds for use in electronic devices iscurrently the subject of intensive research. The aim here is, inparticular, the development of compounds with which improved propertiesof electro-luminescent devices in one or more relevant points can beachieved, such as. for example, power efficiency, lifetime or colourcoordinates of the emitted light.

In accordance with the present invention, the term electroluminescentdevice is taken to mean, inter alia, organic light-emitting transistors(OLETs), organic field-quench devices (OFQDs), organic light-emittingelectrochemical cells (OLECs, LECs or LEECs), organic laser diodes(O-lasers) and organic light-emitting diodes (OLEDs).

Of particular interest is the provision of compounds for use in thelast-mentioned electronic devices called OLEDs. The general structureand the functional principle of OLEDs are known to the person skilled inthe art and are disclosed, inter alia, in U.S. Pat. No. 4,539,507, U.S.Pat. No. 5,151,629, EP 0676461 and WO 1998/27136.

Further improvements are still necessary with respect to the performancedata of OLEDs, in particular with a view to broad commercial use, forexample in display devices or as light sources. Of particular importancein this connection are the lifetime, the efficiency and the operatingvoltage of the OLEDs and the colour values achieved. In addition, it isdesirable, for use as functional materials in electronic devices, forthe compounds to have high thermal stability and a high glass-transitiontemperature and to be sublimable without decomposition.

In this connection, there is, in particular, a need for alternativehole-transport materials. In hole-transport materials in accordance withthe prior art, the voltage generally increases with the layer thicknessof the hole-transport layer. In practice, a greater layer thickness ofthe hole-transport layer would frequently be desirable, but this oftenhas the consequence of a higher operating voltage and worse performancedata. In this connection, there is a need for novel hole-transportmaterials which have high charge-carrier mobility, enabling thickerhole-transport layers to be achieved with an only slight increase in theoperating voltage.

The prior art describes the use of various fluorenes as charge-transportmaterial in electronic and electroluminescent devices.

JP 3824385 B2 discloses 2- and 7-substituted fluorenes which aresubstituted by dibenzofurans or carbazoles.

US 2012/20012832 discloses fluorenes which are substituted by condensedaromatic groups.

WO 2004/020387 discloses fluorenes which are substituted in position 2by an amino group, where the amino group is itself disubstituted by ineach case one phenyl group.

JP 05-303221 discloses the use of 2- and 4-substituted fluorenes asphoto-sensitive compound. The use in electroluminescent devices, such asOLEDs or OLECs, is not described herein.

In spite of the compounds already known, there continues to be a needfor novel hole-transport and hole-injection materials for use in OLEDs.In particular, there is a need for materials with which theabove-mentioned, highly desired improvements in the performance data andproperties of OLEDs can be achieved.

There is likewise a need for novel matrix materials for use in OLEDs andin other electronic devices. In particular, there is a need for matrixmaterials for phosphorescent dopants and for matrix materials formixed-matrix systems, which preferably result in good efficiency, a longlifetime and a low operating voltage of the electronic devices.

The present invention is thus based on the object of providingelectroluminescent devices and compounds which are suitable for use inelectroluminescent devices, such as, for example, OLEDs, and which canbe employed, in particular, as hole-transport materials and/or ashole-injection materials and/or as matrix materials.

As part of the present invention, it has been found, surprisingly, thatcompounds of the formula (1) indicated below are highly suitable for theabove-mentioned uses in electroluminescent devices.

The invention thus relates to an electroluminescent device comprising atleast one compound of the formula (1)

where the following applies to the symbols and indices used:

-   Ar¹, Ar²    -   are on each occurrence, identically or differently, an aromatic        or heteroaromatic group having 10 to 60 aromatic ring atoms,        which may be substituted by one or more radicals R⁴, which are        identical to or different from one another, where the two groups        Ar¹ and Ar² each contain at least two or more aromatic or        heteroaromatic rings;-   R¹    -   is on each occurrence, identically or differently, H, D, F, Cl,        Br, I, C(═O)R⁵, CN, Si(R⁵)₃, NO₂, P(═O)(R⁵)₂, S(═O)R⁵, S(═O)₂R⁵,        a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20        C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group        having 3 to 20 C atoms or an alkenyl or alkynyl group having 2        to 20 C atoms, where the above-mentioned groups may each be        substituted by one or more radicals R⁵ and where one or more CH₂        groups in the above-mentioned groups may be replaced by        —R⁵C═CR⁵—, Si(R⁵)₂, C═O, C═S, C═NR⁵, —C(═O)O—, —C(═O)NR⁵—,        P(═O)(R⁵),—O—, —S—, SO or SO₂ and where one or more H atoms in        the above-mentioned groups may be replaced by D, F, Cl, Br, I,        CN or NO₂, or an aromatic or heteroaromatic ring system having 6        to 30 ring atoms, which may in each case be substituted by one        or more radicals R⁵, or a condensed ring system having 9 to 30        ring atoms, which may in each case be substituted by one or more        radicals R⁵, where, in the case of aromatic or heteroaromatic        condensed rings, not more than 10 ring atoms may be present; the        two radicals R¹ may also form a ring closure with one another,        so that a Spiro compound forms, where no aromatic or        heteroaromatic rings are condensed onto the ring formed by the        two radicals R¹;-   R², R³ and R⁴    -   are on each occurrence, identically or differently, H, D, F, Cl,        Br, I, C(═O)R⁵, CN, Si(R⁵)₃, NO₂, P(═O)(R⁵)₂, S(═O)R⁵, S(═O)₂R⁵,        a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20        C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group        having 3 to 20 C atoms or an alkenyl or alkynyl group having 2        to 20 C atoms, where the above-mentioned groups may each be        substituted by one or more radicals R⁵ and where one or more CH₂        groups in the above-mentioned groups may be replaced by        —R⁵C═CR⁵—, —C≡C—, Si(R⁵)₂, C═O, C═S, C═NR⁵, —C(═O)O—,        —C(═O)NR⁵—, P(═O)(R⁵),—O—, —S—, SO or SO₂ and where one or more        H atoms in the above-mentioned groups may be replaced by D, F,        Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring        system having 6 to 30 ring atoms, which may in each case be        substituted by one or more radicals R⁵;-   R⁵is on each occurrence, identically or differently, H, D, F, Cl,    Br, I, C(═O)R⁶, CN, Si(R⁶)₃, NO₂, P(═O)(R⁶)₂, S(═O)R⁶, S(═O)₂R⁶, a    straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C    atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group    having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20    C atoms, where the above-mentioned groups may each be substituted by    one or more radicals R⁶ and where one or more CH₂ groups in the    above-mentioned groups may be replaced by —R⁶C═CR⁶—, —C≡C—, Si(R⁶)₂,    C═O, C═S, C═NR⁶, —C(═O)O—, —C(═O)NR⁶—, P(═O)(R⁶), —O—, —S—, SO or    SO₂ and where one or more H atoms in the above-mentioned groups may    be replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or    heteroaromatic ring system having 5 to 30 aromatic ring atoms, which    may in each case be substituted by one or more radicals R⁶, or an    aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms,    which may be substituted by one or more radicals R⁶;-   R⁶ is on each occurrence, identically or differently, H, D, F or an    aliphatic, aromatic or heteroaromatic organic radical having 1 to 20    C atoms, in which, in addition, one or more H atoms may be replaced    by D or F;-   n is 0, 1, 2, 3 or 4;-   m is 0, 1, 2 or 3;

with the proviso that the compound of the formula (1), besides the onefluorene group and besides the possible condensed or polycyclic groupsin position 9 of the fluorene, contains no further polycyclic orcondensed groups.

The numbering on the fluorene is defined as follows.

Preference is given to an electroluminescent device which comprises atleast one compound of the formula (1) in which the two radicals R¹ areidentical.

It is preferred for the electroluminescent device to comprise at leastone compound of the formula (1) which is characterised in that m isequal to 1 or 0, very preferably m is equal to 0.

It is furthermore preferred for the electroluminescent device tocomprise at least one compound of the formula (1) which is characterisedin that n is equal to 2, 1 or 0, very preferably n is equal to 0 or 1.

The compound of the formula (1) is preferably selected from a compoundof the formula (2),

where the symbols are defined as indicated above.

Most preference is given to a compound of the formula (2) in which thetwo radicals R¹ are identical.

In a furthermore preferred embodiment of the present invention, theelectroluminescent device comprises at least one compound of the formula(3), where preference is furthermore given to a compound of the formula(3) in which the radicals R¹ are identical.

In a very preferred embodiment of the present invention, R² is equal toH or a straight-chain alkyl group having 1 to 20 C atoms or a branchedor cyclic alkyl group having 3 to 20 C atoms, where the above-mentionedgroups may each be substituted by one or more radicals R⁵ and where oneor more H atoms in the above-mentioned groups may be replaced by D, F,Cl, Br, I, CN or NO₂, or an aromatic ring system having 6 to 30 aromaticring atoms, which may in each case be substituted by one or moreradicals R⁵.

R² is particularly preferably equal to H or an aromatic ring systemhaving 6 to 30 aromatic ring atoms, which may in each case besubstituted by one or more radicals R⁵.

In a very particularly preferred embodiment, the electroluminescentdevice comprises at least one compound of the formula (3) in which R² isequal to H and the two R¹ are, identically to or differently from oneanother, preferably identically, an aromatic or heteroaromatic ringsystem having 6 to 30 aromatic ring atoms, which may in each case besubstituted by one or more radicals R⁵.

R² in the formulae (1) to (3) is especially preferably equal to phenyl,biphenyl, terphenyl or quaterphenyl, each of which may be substituted byone or more radicals R⁵, where it is furthermore preferred for these tobe unsubstituted, or H.

In a further very particularly preferred embodiment, theelectroluminescent device comprises at least one compound of the formula(3) in which R² is an aromatic ring system having 6 to 30 aromatic ringatoms, which may in each case be substituted by one or more radicals R⁵,and R¹ is, identically to or differently from one another, preferablyidentically, a straight-chain alkyl group having 1 to 20 C atoms or abranched or cyclic alkyl group having 3 to 20 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR⁵ and where one or more H atoms in the above-mentioned groups may bereplaced by D, F, Cl, Br, I, CN or NO₂.

It is furthermore preferred for the electroluminescent device tocomprise at least one compound of the formula (4),

in which X is, identically or differently on each occurrence, N or CR⁴,where only 3 of the groups X per ring may be N. It is very preferred forX in formula (4) to be equal to CR⁴, where the above definitions applyto the radicals R¹, R² and R⁴.

Preferred radicals Ar¹ and Ar² are selected from the radicals having theformulae (5) to (60) shown in the following table, where the radicalsmay be substituted, as already indicated above, by one or more radicalsR⁴, which are identical to or different from one another;

Preference is given in the sense of the present invention to anelectroluminescent device which comprises at least one compound of theformula (1) in which Ar¹ and Ar² contain only aromatic rings, but notheteroaromatic rings.

Ar¹ and Ar² are especially preferably, identically or differently,biphenyl, terphenyl or quaterphenyl, each of which may be substituted byone or more radicals R⁴, where it is furthermore preferred for these tobe unsubstituted.

In a furthermore very preferred embodiment of the present invention, inthe compound of the formula (1),

the two radicals R¹

-   -   are identical and are selected from a straight-chain alkyl,        alkoxy or thioalkyl group having 1 to 20 C atoms or a branched        or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C        atoms, where the above-mentioned groups may each be substituted        by one or more radicals R⁵ and where one or more H atoms in the        above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or        NO₂, or an aromatic or heteroaromatic ring system having 6 to 30        ring atoms, which may in each case be substituted by one or more        radicals R⁵, or a condensed ring system having 9 to 30 ring        atoms, which may in each case be substituted by one or more        radicals R⁵, where, in the case of aromatic or heteroaromatic        condensed rings, not more than 10 ring atoms may be present; the        two radicals R¹ may also form a ring closure with one another,        so that a Spiro compound forms, where no aromatic or        heteroaromatic rings are condensed onto the ring formed by the        two radicals R¹;

-   is equal to 1 and the radical R² is in position 7 of the fluorene;

-   m is equal to 0;

-   R² is equal to an alkyl group having 1 to 20 C atoms or a branched    or cyclic alkyl group having 3 to 20 C atoms, a pyridyl, phenyl,    biphenyl, terphenyl or quaterphenyl group, where the groups may be    substituted by one or more radicals R⁵, where it is furthermore    preferred for the aromatic or heteroaromatic group to be    unsubstituted, or is equal to H;

-   Ar¹ and Ar²    -   are identical or different and are selected from biphenyl,        terphenyl and quaterphenyl, each of which may be substituted by        one or more radicals R⁴, where it is furthermore preferred for        these to be unsubstituted.

In a furthermore very preferred embodiment of the present invention, inthe compound of the formula (1),

-   the two radicals R¹    -   are identical and are selected from a straight-chain alkyl group        having 1 to 20 C atoms or a branched or cyclic alkyl group        having 3 to 20 C atoms, where the groups may each be substituted        by one or more radicals R⁵ and where one or more H atoms in the        above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or        NO₂;-   n is equal to 1 and the radical R² is in position 7 of the fluorene;-   m is equal to 0;-   R² is equal to H or an alkyl group having 1 to 20 C atoms or a    branched or cyclic alkyl group having 3 to 20 C atoms, where the    groups may be substituted by one or more radicals R⁵, where R² is    preferably equal to H;-   Ar¹ and Ar²    -   are identical or different and are selected from biphenyl,        terphenyl and quaterphenyl, each of which may be substituted by        one or more radicals R⁴, where it is furthermore preferred for        these to be unsubstituted.

In a furthermore very preferred embodiment of the present invention, inthe compound of the formula (1),

-   the two radicals R¹    -   are identical and are selected from a straight-chain alkyl group        having 1 to 20 C atoms or a branched or cyclic alkyl group        having 3 to 20 C atoms, where the groups may each be substituted        by one or more radicals R⁵ and where one or more H atoms in the        above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or        NO₂;-   n is equal to 1 and the radical R² is in position 7 of the fluorene;-   is equal to 0;-   R² is equal to a pyridyl, phenyl, biphenyl, terphenyl or    quaterphenyl group, where the groups may be substituted by one or    more radicals R⁵, where it is furthermore preferred for the aromatic    or hetero-aromatic group to be unsubstituted;-   Ar¹ and Ar²    -   are identical or different and are selected from biphenyl,        terphenyl and quaterphenyl, each of which may be substituted by        one or more radicals R⁴, where it is furthermore preferred for        these to be unsubstituted.

In a furthermore very preferred embodiment of the present invention, inthe compound of the formula (1),

-   the two radicals R¹    -   are identical and are selected from an aromatic or        heteroaromatic ring system having 6 to 30 ring atoms, which may        in each case be substituted by one or more radicals R⁵, or a        condensed ring system having 9 to 30 ring atoms, which may in        each case be substituted by one or more radicals R⁵, where, in        the case of aromatic or heteroaromatic condensed rings, not more        than 10 ring atoms may be present;-   n is equal to 1 and the radical R² is in position 7 of the fluorene;-   is equal to 0;-   R² is equal to an alkyl group having 1 to 20 C atoms or a branched    or cyclic alkyl group having 3 to 20 C atoms, a pyridyl, phenyl,    biphenyl, terphenyl or quaterphenyl group, where the groups may be    substituted by one or more radicals R⁵, where it is furthermore    preferred for the aromatic or heteroaromatic group to be    unsubstituted, or is equal to H, where R² is preferably equal to H;-   Ar¹ and Ar²    -   are identical or different and are selected from biphenyl,        terphenyl and quaterphenyl, each of which may be substituted by        one or more radicals R⁴, where it is furthermore preferred for        these to be unsubstituted.

Preference is furthermore given in the sense of the present invention toan electroluminescent device which comprises at least one compound ofthe formula (1) which, besides the one fluorene group, contains nofurther polycyclic or condensed groups.

The compounds according to the invention can be synthesised by processeswhich are known to the person skilled in the art from the prior art. Thepreparation can be carried out, for example, by means of halogenation,Buchwald coupling and Suzuki coupling.

The following scheme shows a preferred synthetic route for thepreparation of the compounds of the formula (1) according to theinvention. For the synthesis of the compounds according to theinvention, the fluorene compound A is reacted with an amine B of theformula Ar¹—NH—Ar² in a Buchwald coupling

Another preferred synthetic route for the preparation of the compoundsaccording to the invention is depicted in the following scheme. Thecarboxylate groups in compound C are converted into the correspondingalcohol D by the addition reaction of an alkyl- or aryl-metal compound,for example an alkyl- or aryllithium compound or an alkyl- oraryl-Grignard compound. This alcohol can be cyclised under acidicconditions to give compound E. Finally, a Buchwald coupling to an amineB of the formula Ar¹—NH—Ar² is carried out

The following scheme shows a further preferred synthetic route for thepreparation of compounds according to the invention. For this purpose,the fluorene A is reacted with a boronic acid F of the formulaAr³—B(OH)₂ in a Suzuki coupling. Bromination of the resultant compoundsusing, for example, bromine followed by a Buchwald coupling to an amineof the formula Ar¹—NH—Ar² gives the corresponding compounds according tothe invention.

Synthetic routes for the starting compounds A, B and C which areemployed in the synthesis of the compounds according to the inventionare known to the person skilled in the art. Furthermore, some explicitsynthetic processes are described in detail in the working examples.

Preferred coupling reactions here are Buchwald couplings.

The compounds described above, in particular compounds which aresubstituted by reactive leaving groups, such as bromine, iodine,chlorine, boronic acid or boronic acid ester, can be used as monomersfor the production of corresponding oligomers, dendrimers or polymers.The oligomerisation or polymerisation here preferably takes place viathe halogen functionality or the boronic acid functionality.

Preferred compounds which are used in the electroluminescent devicesaccording to the invention are shown by way of example in the followingtable,

The present invention also relates to compounds of the general formula(167)

where the following applies to the symbols used in formula (167)

-   Ar³, Ar⁴    -   are on each occurrence, identically or differently, an aromatic        or heteroaromatic ring system having 10 to 60 ring atoms, which        may be substituted by one or more radicals R⁵, which are        identical to or different from one another, where the two groups        Ar³ and Ar⁴ each contain at least two or more aromatic or        heteroaromatic, preferably aromatic, rings;

R⁷ is identical on each occurrence and is selected from the groupconsisting of a straight-chain alkyl, alkoxy or thioalkyl group having 1to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl grouphaving 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 Catoms, where the above-mentioned groups may each be substituted by oneor more radicals R⁵ and where one or more H atoms in the above-mentionedgroups may be replaced by D, CN or NO₂, or an aromatic or heteroaromaticring system having 6 to 30 ring atoms, which may in each case besubstituted by one or more radicals R⁵, where R⁵ is defined as indicatedabove, or a condensed ring system having 9 to 30 ring atoms, which mayin each case be substituted by one or more radicals R⁵, where, in thecase of aromatic or heteroaromatic condensed rings, not more than 10ring atoms may be present in the condensed ring system; the two radicalsR⁷ may also form a ring closure with one another, so that a spirocompound forms, where no aromatic or heteroaromatic rings are condensedonto the ring formed by the two radicals R⁷, and where, if R⁷ is astraight-chain or branched alkyl group, R⁵ is an aromatic orheteroaromatic ring system having 6 to 30 ring atoms, which may in eachcase be substituted by one or more radicals R⁵, and where R⁵ is definedas indicated above;

-   R⁸ is H, D or an aromatic or heteroaromatic ring system having 6 to    30 ring atoms, which may in each case be substituted by one or more    radicals R⁵, where R⁵ is defined as indicated above and where, if R⁸    is equal to H, R⁷ is an aromatic or heteroaromatic ring system    having 6 to 30 aromatic ring atoms, which may in each case be    substituted by one or more radicals R⁵, where R⁵ is defined as    indicated above;-   a is either 1, 2, 3 or 4, preferably 1 or 2, very preferably 1;

with the proviso that the compound of the formula (167), besides the onefluorene group and besides the possible condensed or polycyclic groupsin position 9 of the fluorene, contains no further polycyclic orcondensed groups

and with the proviso that the compound contains no halogens.

It is preferred for the compound of the formula (167) to contain nofurther polycyclic or condensed groups besides the one fluorene group.

Compounds of the formula (167) where a=1 and R⁸ is in position 7 of thefluorene are preferred, i.e. compounds of the formula (168)

Particular preference is given to compounds of the formulae (167) and(168) where the following applies to the symbols used:

-   Ar³, Ar⁴    -   are selected on each occurrence, identically or differently,        from biphenyl, terphenyl and quaterphenyl, each of which may be        substituted by one or more radicals R⁵, where it is furthermore        preferred for these to be unsubstituted;-   R⁷ is identical on each occurrence and is selected from an aromatic    or heteroaromatic ring system having 6 to 30 ring atoms, which may    in each case be substituted by one or more radicals R⁵, where R⁵ is    defined as indicated above, or a condensed ring system having 9 to    30 ring atoms, which may in each case be substituted by one or more    radicals R⁵, where, in the case of aromatic or heteroaromatic    condensed rings, not more than 10 ring atoms may be present in the    condensed ring system;

with the proviso that the compound of the formula (168), besides the onefluorene group and besides the possible condensed or polycyclic groupsin position 9 of the fluorene, contains no further polycyclic orcondensed groups and with the proviso that the compound contains nohalogens.

Furthermore preferred compounds of the formula (167) are those of thegeneral formula (169)

where X is, identically or differently on each occurrence, N or CR⁵ andR⁵, Ar³ and Ar⁴ are defined as indicated above. It is preferred for X informula (169) to be equal to CR⁵.

Ar¹ and Ar³ in formula (169) are preferably selected on each occurrence,identically or differently, from biphenyl, terphenyl and quaterphenyl,each of which may be substituted by one or more radicals R⁵, where it isfurthermore preferred for these to be unsubstituted.

Most preference is given to compounds of the formula (170)

Ar¹ and Ar³ in formula (170) are preferably selected on each occurrence,identically or differently, from biphenyl, terphenyl and quaterphenyl,each of which may be substituted by one or more radicals R⁵, where it isfurthermore preferred for these to be unsubstituted.

In a further preferred embodiment of the present invention, the compoundis selected from the general formula (171)

where the above definitions apply to the symbols used. Ar¹ and Ar³ informula (171) are preferably selected on each occurrence, identically ordifferently, from biphenyl, terphenyl and quaterphenyl, each of whichmay be substituted by one or more radicals R⁵, where it is furthermorepreferred for these to be unsubstituted.

Furthermore preferred compounds of the formula (5) are compounds of theformula (172)

where the following applies to the symbols used:

-   X is, identically or differently on each occurrence, N or CR⁵ and    preferably CR⁵, and R⁵ is defined as indicated above;-   R⁷ is a straight-chain alkyl group having 1 to 20 C atoms or a    branched or cyclic alkyl group having 3 to 20 C atoms, where the    above-mentioned groups may each be substituted by one or more    radicals R⁵ and where one or more H atoms in the above-mentioned    groups may be replaced by D, CN or NO₂, where the two radicals R⁷    may also form a ring closure, so that a spiro compound forms, where    no aromatic or heteroaromatic rings are condensed onto the ring    formed by the two radicals R⁷;

and where Ar³ and Ar⁴ are defined as indicated above.

Ar¹ and Ar³ in formula (172) are preferably selected on each occurrence,identically or differently, from biphenyl, terphenyl and quaterphenyl,each of which may be substituted by one or more radicals R⁵, where it isfurthermore preferred for these to be unsubstituted.

In a furthermore preferred embodiment of the present invention, thecompound is selected from the general formula (173)

where the following applies to the symbols used:

-   R⁷ is a straight-chain alkyl group having 1 to 20 C atoms or a    branched or cyclic alkyl group having 3 to 20 C atoms, where the    above-mentioned groups may each be substituted by one or more    radicals R⁵ and where one or more H atoms in the above-mentioned    groups may be replaced by D, CN or NO₂, where the two radicals R⁷    may also form a ring closure, so that a spiro compound forms, where    no aromatic or heteroaromatic rings are condensed onto the ring    formed by the two radicals R⁷.

Ar¹ and Ar³ in formula (173) are preferably selected on each occurrence,identically or differently, from biphenyl, terphenyl and quaterphenyl,each of which may be substituted by one or more radicals R⁵, where it isfurthermore preferred for these to be unsubstituted.

Very particular preference is given to compounds of the followingformulae (174) to (236) shown by way of example:

The compounds according to the invention can be employed as compositionswith other organically functional materials which are used in electronicdevices. A large number of possible organically functional materials isknown to the person skilled in the art from the prior art. The presentinvention therefore also relates to a composition comprising one or morecompounds of the formula (167) according to the invention and at leastone further organically functional material selected from the groupconsisting of fluorescent emitters, phosphorescent emitters, hostmaterials, matrix materials, electron-transport materials,electron-injection materials, hole-conductor materials, hole-injectionmaterials, electron-blocking materials and hole-blocking materials.

For the processing of the compounds according to the invention from theliquid phase, for example by spin coating or by printing processes,formulations of the compounds according to the invention are necessary.These formulations can be, for example, solutions, dispersions ormini-emulsions. It may be preferred to use mixtures of two or moresolvents for this purpose. Suitable and preferred solvents are, forexample, toluene, anisole, o-, m- or p-xylene, methyl benzoate,dimethylanisole, mesitylene, tetralin, veratrol, THF, methyl-THF, THP,chlorobenzene, dioxane or mixtures of these solvents.

The invention therefore furthermore relates to a formulation, inparticular a solution, dispersion or mini-emulsion, comprising at leastone compound of the formula (167) or at least one polymer, oligomer ordendrimer containing at least one unit of the formula (167), and atleast one solvent, preferably an organic solvent. The way in whichsolutions of this type can be prepared is known to the person skilled inthe art and is described, for example, in WO 2002/072714, WO 2003/019694and the literature cited therein.

The compounds according to the invention are suitable for use inelectronic devices, in particular in organic electroluminescent devices(for example OLEDs or OLECs). Depending on the substitution, thecompounds are employed in different functions and layers.

The present invention therefore furthermore relates to the use of thecompounds of the formula (167) in electronic devices and to electronicdevices themselves which comprise one or more compounds of the formula(167). The electronic devices here are preferably selected from thegroup consisting of organic integrated circuits (OICs), organicfield-effect transistors (OFETs), organic thin-film transistors (OTFTs),organic light-emitting transistors (OLETs), organic solar cells (OSCs),organic optical detectors, organic photoreceptors, organic field-quenchdevices (OFQDs), organic light-emitting electrochemical cells (OLECs),organic laser diodes (O-lasers) and particularly preferably organicelectroluminescent devices (OLEDs and OLECs).

The invention relates, as already stated above, to electronic devicescomprising at least one compound of the formula (167). The electronicdevices here are preferably selected from the devices mentioned above.Particular preference is given to organic electroluminescent devices(OLEDs) comprising anode, cathode and at least one emitting layer,characterised in that at least one organic layer, which may be anemitting layer, a hole-transport layer or another layer, comprises atleast one compound of the formula (167).

An aryl group in the sense of this invention contains 6 to 60 aromaticring atoms; a heteroaryl group in the sense of this invention contains 5to 60 aromatic ring atoms, at least one of which is a heteroatom. Theheteroatoms are preferably selected from N, O and S. This represents thebasic definition. If other preferences are indicated in the descriptionof the present invention, for example with respect to the number ofaromatic ring atoms or the heteroatoms present, these apply.

An aryl group or heteroaryl group here is taken to mean either a simplearomatic ring, i.e. benzene, or a simple heteroaromatic ring, forexample pyridine, pyrimidine or thiophene, or a condensed (annellated)aromatic or heteroaromatic polycycle, for example naphthalene,phenanthrene, quinoline or carbazole. A condensed (annellated) aromaticor heteroaromatic polycycle in the sense of the present applicationconsists of two or more simple aromatic or heteroaromatic ringscondensed with one another.

An aryl or heteroaryl group, which may in each case be substituted bythe above-mentioned radicals and which may be linked to the aromatic orhetero-aromatic ring system via any desired positions, is taken to mean,in particular, groups derived from benzene, naphthalene, anthracene,phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene,benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene,furan, benzofuran, isobenzofuran, dibenzofuran, thiophene,benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole,isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine,phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,pyrimidine, benzo-pyrimidine, quinoxaline, pyrazine, phenazine,naphthyridine, azacarbazole, benzocarboline, phenanthroline,1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine,1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine,1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine andbenzothiadiazole.

An aryloxy group in accordance with the definition of the presentinvention is taken to mean an aryl group, as defined above, which isbonded via an oxygen atom. An analogous definition applies toheteroaryloxy groups.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 5 to 60 aromatic ring atoms, at least one ofwhich is a heteroatom. The heteroatoms are preferably selected from N, Oand/or S. An aromatic or heteroaromatic ring system in the sense of thisinvention is intended to be taken to mean a system which does notnecessarily contain only aryl or heteroaryl groups, but instead inwhich, in addition, a plurality of aryl or heteroaryl groups may beconnected by a non-aromatic unit (preferably less than 10% of the atomsother than H), such as, for example, an sp³-hybridised C, Si, N or Oatom, an sp²-hybridised C or N atom or an sp-hybridised C atom. Thus,for example, systems such as 9,9′-spirobifluorene, 9,9′-diarylfluorene,triarylamine, diaryl ether, stilbene, etc., are also intended to betaken to be aromatic ring systems in the sense of this invention, as aresystems in which two or more aryl groups are connected, for example, bya linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group.Furthermore, systems in which two or more aryl or heteroaryl groups arelinked to one another via single bonds are also taken to be aromatic orheteroaromatic ring systems in the sense of this invention, such as, forexample, systems such as biphenyl, terphenyl or diphenyltriazine.

An aromatic or heteroaromatic ring system having 5-60 aromatic ringatoms, which may in each case also be substituted by radicals as definedabove and which may be linked to the aromatic or heteroaromatic groupvia any desired positions, is taken to mean, in particular, groupsderived from benzene, naphthalene, anthracene, benzanthracene,phenanthrene, benzophenanthrene, pyrene, chrysene, perylene,fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl,biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene,spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene,cis- or trans-indenofluorene, truxene, isotruxene, spirotruxene,spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, carbazole, indolocarbazole, indenocarbazole,pyridine, quinoline, isoquinoline, acridine, phenanthridine,benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,phenothiazine, phenoxazine, pyrazole. indazole, imidazole,benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole,pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole,naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole,1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine,benzo-pyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene,2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole, or combinations ofthese groups.

For the purposes of the present invention, a straight-chain alkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, inwhich, in addition, individual H atoms or CH₂ groups may be substitutedby the groups mentioned above under the definition of the radicals, ispreferably taken to mean the radicals methyl, ethyl, n-propyl, i-propyl,n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl,cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl,cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl,pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl,pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl,cyclo-heptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl,pentynyl, hexynyl or octynyl. An alkoxy or thioalkyl group having 1 to40 C atoms is preferably taken to mean methoxy, trifluoromethoxy,ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy,n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy,n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy,pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio,n-propylthio, i-propylthio, n-butylthio, i-butylthio. s-butylthio,t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio,n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio,2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio,2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio,pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio,heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio,ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio,heptynylthio or octynylthio.

The compounds of the formula (1) described above may be substituted byreactive leaving groups, such as bromine, iodine, chlorine, boronic acidor boronic acid ester. These can be used as monomers for the productionof corresponding oligomers, dendrimers or polymers. Suitable reactiveleaving groups are, for example, bromine, iodine, chlorine, boronicacids, boronic acid esters, amines, alkenyl or alkynyl groups having aterminal C-C double bond or C-C triple bond, oxiranes, oxetanes, groupswhich undergo a cycloaddition, for example a 1,3-dipolar cycloaddition,such as, for example, dienes or azides, carboxylic acid derivatives,alcohols and silanes.

The invention therefore furthermore relates to oligomers, polymers ordendrimers containing one or more compounds of the formula (1), wherethe bond(s) to the polymer, oligomer or dendrimer may be localised atany desired possible positions in formula (1). Depending on the linkingof the compound of the formula (1), the compound is a constituent of aside chain of the oligomer or polymer or a constituent of the mainchain. An oligomer in the sense of this invention is taken to mean acompound which is built up from at least three monomer units. A polymerin the sense of the invention is taken to mean a compound which is builtup from at least ten monomer units. The polymers, oligomers ordendrimers according to the invention may be conjugated, partiallyconjugated or non-conjugated. The oligomers or polymers according to theinvention may be linear, branched or dendritic. In the structures linkedin a linear manner, the units of the formula (1) may be linked directlyto one another or they may be linked to one another via a divalentgroup, for example via a substituted or unsubstituted alkylene group,via a heteroatom or via a divalent aromatic or heteroaromatic group. Inbranched and dendritic structures, for example, three or more units ofthe formula (1) may be linked via a trivalent or polyvalent group, forexample via a trivalent or polyvalent aromatic or heteroaromatic group,to form a branched or dendritic oligomer or polymer.

The same preferences as described above for compounds of the formula (1)apply to the recurring units of the formula (1) in oligomers, dendrimersand polymers.

For the preparation of the oligomers or polymers, the monomers accordingto the invention are homopolymerised or copolymerised with furthermonomers. Suitable and preferred comonomers are selected from fluorenes(for example in accordance with EP 842208 or WO 2000/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 2006/061181), para-phenylenes (for example in accordance with WO1992/18552), carbazoles (for example in accordance with WO 2004/070772or WO 2004/113468), thiophenes (for example in accordance with EP1028136), dihydrophenanthrenes (for example in accordance with WO2005/014689 or WO 2007/006383), cis- and trans-indenofluorenes (forexample in accordance with WO 2004/041901 or WO 2004/113412), ketones(for example in accordance with WO 2005/040302), phenanthrenes (forexample in accordance with WO 2005/104264 or WO 2007/017066) or also aplurality of these units. The polymers, oligomers and dendrimers usuallyalso contain further units, for example emitting (fluorescent orphosphorescent) units, such as, for example, vinyltriarylamines (forexample in accordance with WO 2007/068325) or phosphorescent metalcomplexes (for example in accordance with WO 2006/003000), and/orcharge-transport units, in particular those based on triarylamines.

The polymers, oligomers and dendrimers according to the invention haveadvantageous properties, in particular long lifetimes, high efficienciesand good colour coordinates.

The polymers and oligomers according to the invention are generallyprepared by polymerisation of one or more types of monomer, at least onemonomer of which results in recurring units of the formula (1) in thepolymer. Suitable polymerisation reactions are known to the personskilled in the art and are described in the literature. Particularlysuitable and preferred polymerisation reactions which result in C—C orC—N links are the following:

-   (A) SUZUKI polymerisation;-   (B) YAMAMOTO polymerisation;-   (C) STILLE polymerisation; and-   (D) HARTWIG-BUCHWALD polymerisation.

The way in which the polymerisation can be carried out by these methodsand the way in which the polymers can then be separated off from thereaction medium and purified is known to the person skilled in the artand is described in detail in the literature, for example in WO2003/048225, WO 2004/037887 and WO 2004/037887.

The present invention thus also relates to a process for the preparationof the polymers, oligomers and dendrimers according to the invention,which is characterised in that they are prepared by SUZUKIpolymerisation, YAMAMOTO polymerisation, STILLE polymerisation orHARTWIG-BUCHWALD polymerisation. The dendrimers according to theinvention can be prepared by processes known to the person skilled inthe art or analogously thereto. Suitable processes are described in theliterature, such as, for example, in Frechet, Jean M. J.; Hawker, CraigJ., “Hyperbranched polyphenylene and hyperbranched polyesters: newsoluble, three-dimensional, reactive polymers”, Reactive & FunctionalPolymers (1995), 26(1-3), 127-36; Janssen, H. M.; Meijer, E. W., “Thesynthesis and characterization of dendritic molecules”, MaterialsScience and Technology (1999), 20 (Synthesis of Polymers), 403-458;Tomalia, Donald A., “Dendrimer molecules”, Scientific American (1995),272(5), 62-6; WO 2002/067343 A1 and WO 2005/026144 A1.

Apart from the cathode, anode and emitting layer, the organicelectroluminescent device may also comprise further layers. These areselected, for example, from in each case one or more hole-injectionlayers, hole-transport layers, hole-blocking layers, electron-transportlayers, electron-injection layers, electron-blocking layers.exciton-blocking layers, interlayers, charge-generation layers (IDMC2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K.Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL DeviceHaving Charge Generation Layer) and/or Organic or in-organic pinjunctions. However, it should be pointed out that each of these layersdoes not necessarily have to be present and the choice of layers isalways dependent on the compounds used and in particular also on whetherthe electroluminescent device is fluorescent or phosphorescent.

The organic electroluminescent device according to the invention maycomprise a plurality of emitting layers. These emission layers in thiscase particularly preferably have in total a plurality of emissionmaxima between 380 nm and 750 nm, resulting overall in white emission,i.e. various emitting compounds which are able to fluoresce orphosphoresce and which emit blue or yellow or orange or red light areused in the emitting layers. Particular preference is given tothree-layer systems, i.e. systems having three emitting layers, wherethe three layers exhibit blue, green and orange or red emission (for thebasic structure see, for example, WO 2005/011013). The compoundsaccording to the invention may be present in such devices in ahole-transport layer, an emitting layer and/or in another layer. Itshould be noted that, for the generation of white light. an emittercompound used individually which emits in a broad wavelength range mayalso be suitable instead of a plurality of emitter compounds emitting ina colour.

It is preferred in accordance with the invention for the compound of theformula (1) to be employed in an electroluminescent device comprisingone or more phosphorescent dopants. The compound can be used in variouslayers here, preferably in an hole-transport layer, a hole-injectionlayer or in an emitting layer. However, the compound of the formula (1)can also be employed in accordance with the invention in an electronicdevice comprising one or more fluorescent dopants.

The term phosphorescent dopants typically encompasses compounds in whichthe light emission takes place by a spin-forbidden transition, forexample a transition from an excited triplet state or a state having arelatively high spin quantum number, for example a quintet state.

Suitable phosphorescent dopants (=triplet emitters) are, in particular;compounds which emit light, preferably in the visible region, onsuitable excitation and in addition contain at least one atom having anatomic number greater than 20, preferably greater than 38 and less than84, particularly preferably greater than 56 and less than 80. Thephosphorescent emitters used are preferably compounds which containcopper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium,iridium, palladium, platinum, silver, gold or europium, in particularcompounds which contain iridium, platinum or copper.

For the purposes of the present invention, all luminescent iridium,platinum or copper complexes are regarded as phosphorescent compounds.

Examples of the emitters described above are revealed by theapplications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614, WO 05/033244, WO 2005/019373 and US2005/0258742. In general, all phosphorescent complexes as used inaccordance with the prior art for phosphorescent OLEDs and as are knownto the person skilled in the art in the area of organicelectroluminescent devices are suitable. The person skilled in the artwill also be able to employ further phosphorescent complexes withoutinventive step in combination with the compounds of the formula (1) inorganic electroluminescent devices.

Explicit examples of suitable phosphorescent emitter compounds arefurthermore revealed by the following table.

In a preferred embodiment of the invention, the compounds of the formula(1) or (167) are employed as hole-transport material. The compounds arethen preferably employed in a hole-transport layer and/or in ahole-injection layer. A hole-injection layer in the sense of thisinvention is a layer which is directly adjacent to the anode. Ahole-transport layer in the sense of this invention is a layer which islocated between the hole-injection layer and the emission layer. Thehole-transport layer may be directly adjacent to the emission layer. Ifthe compounds of the formula (1) are used as hole-transport material oras hole-injection material, it may be preferred for them to be dopedwith electron-acceptor compounds, for example with F₄-TCNQ or compoundsas described in EP 1476881 or EP 1596445. In a further preferredembodiment of the invention, a compound of the formula (1) is used ashole-transport material in combination with a hexaazatriphenylenederivative, as described in US 2007/0092755. The hexaazatriphenylenederivative here is particularly preferably employed in a separate layer.

If the compounds of the formula (1) or (167) are employed ashole-transport material in a hole-transport layer, the compound may beemployed as pure material, i.e. in a proportion of 100%, in thehole-transport layer, or it may be employed in combination with one ormore further compounds in the hole-transport layer.

In a further embodiment of the present invention, the compounds of theformula (1) or (167) are employed as emitting materials. For thispurpose, the compounds are preferably employed in an emission layer.Besides at least one of the compounds of the formula (1) or (167), theemission layer furthermore comprises at least one host material. Theperson skilled in the art will be able to make a selection from theknown host materials without difficulties and without being inventive.

In a further embodiment of the present invention, the compounds of theformula (1) or (167) are employed as matrix material in combination withone or more dopants, preferably phosphorescent dopants.

A dopant in a system comprising a matrix material and a dopant is takento mean the component whose proportion in the mixture is the smaller.Correspondingly, a matrix material is taken to mean the component whoseproportion in the mixture is the greater in a system comprising a matrixmaterial and a dopant.

The proportion of the matrix material in the emitting layer is in thiscase between 50.0 and 99.9% by vol., preferably between 80.0 and 99.5%by vol. and particularly preferably between 92.0 and 99.5% by vol. forfluorescent emitting layers and between 85.0 and 97.0% by vol. forphosphorescent emitting layers.

Correspondingly, the proportion of the dopant is between 0.1 and 50.0%by vol., preferably between 0.5 and 20.0% by vol. and particularlypreferably between 0.5 and 8.0% by vol. for fluorescent emitting layersand between 3.0 and 15.0% by vol. for phosphorescent emitting layers.

An emitting layer of an organic electroluminescent device may alsocomprise systems comprising a plurality of matrix materials(mixed-matrix systems) and/or a plurality of dopants. In this case too,the dopants are generally the materials whose proportion in the systemis the smaller and the matrix materials are the materials whoseproportion in the system is the greater. In individual cases, however,the proportion of an individual matrix material in the system may besmaller than the proportion of an individual dopant.

In a further preferred embodiment of the invention, the compounds of theformulae (1) or (167) are used as a component of mixed-matrix systems.The mixed-matrix systems preferably comprise two or three differentmatrix materials, particularly preferably two different matrixmaterials. One of the two materials here is preferably a material havinghole-transporting properties and the other material is a material havingelectron-transporting properties. However, the desiredelectron-transporting and hole-transporting properties of themixed-matrix components may also be combined principally or completelyin a single mixed-matrix components, where the further mixed-matrixcomponent(s) fulfil other functions. The two different matrix materialshere may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1,particularly preferably 1:10 to 1:1 and very particularly preferably 1:4to 1:1. Mixed-matrix systems are preferably employed in phosphorescentorganic electroluminescent devices. More precise information onmixed-matrix systems is given, inter alia, in the application WO2010/108579.

The mixed-matrix systems may comprise one or more dopants, preferablyone or more phosphorescent dopants. In general, mixed-matrix systems arepreferably employed in phosphorescent organic electroluminescentdevices.

Particularly suitable matrix materials which can be used as matrixcomponents of a mixed-matrix system in combination with the compoundsaccording to the invention are selected from the preferred matrixmaterials for phosphorescent dopants indicated below or the preferredmatrix materials for fluorescent dopants, depending on what type ofdopant is employed in the mixed-matrix system.

Preferred phosphorescent dopants for use in mixed-matrix systems are thephosphorescent dopants shown in the above table.

The materials preferably employed in the relevant functions in thedevices according to the invention are indicated below.

Preferred fluorescent dopants are selected from the class of thearylamines. An arylamine or aromatic amine in the sense of thisinvention is taken to mean a compound which contains three substitutedor unsubstituted aromatic or heteroaromatic ring systems bonded directlyto the nitrogen. At least one of these aromatic or heteroaromatic ringsystems is preferably a condensed ring system, particularly preferablyhaving at least 14 aromatic ring atoms. Preferred examples thereof arearomatic anthracenamines, aromatic anthracenediamines, aromaticpyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromaticchrysenediamines. An aromatic anthracenamine is taken to mean a compoundin which one diarylamino group is bonded directly to an anthracenegroup, preferably in the 9-position. An aromatic anthracenediamine istaken to mean a compound in which two diarylamino groups are bondeddirectly to an anthracene group, preferably in the 9,10-position.Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediaminesare defined analogously thereto, where the diarylamino groups arepreferably bonded to the pyrene in the 1-position or in the1,6-position.

Suitable matrix materials, preferably for fluorescent dopants, besidesthe compounds according to the invention, are materials from variousclasses of substance. Preferred matrix materials are selected from theclasses of the oligoarylenes (for example2,2′,7,7′-tetraphenylspirobifluorene in accordance with EP 676461 ordinaphthylanthracene), in particular the oligoarylenes containingcondensed aromatic groups, the oligoarylenevinylenes (for example DPVBior spiro-DPVBi in accordance with EP 676461), the polypodal metalcomplexes (for example in accordance with WO 2004/081017), thehole-conducting compounds (for example in accordance with WO2004/058911), the electron-conducting compounds, in particular ketones,phosphine oxides, sulfoxides, etc. (for example in accordance with WO2005/084081 and WO 20051084082), the atropisomers (for example inaccordance with WO 2006/048268), the boronic acid derivatives (forexample in accordance with WO 2006/117052) or the benzanthracenes (forexample in accordance with WO 2008/145239). Particularly preferredmatrix materials are selected from the classes of the oligoarylenes,comprising naphthalene, anthracene, benzanthracene and/or pyrene oratropisomers of these compounds, the oligoarylenevinylenes, the ketones,the phosphine oxides and the sulfoxides. Very particularly preferredmatrix materials are selected from the classes of the oligoarylenes,comprising anthracene, benzanthracene, benzophenanthrene and/or pyreneor atropisomers of these compounds. An oligoarylene in the sense of thisinvention is intended to be taken to mean a compound in which at leastthree aryl or arylene groups are bonded to one another.

Preferred matrix materials for phosphorescent dopants, besides thecompounds according to the invention, are aromatic amines, in particulartriarylamines, for example in accordance with US 2005/0069729, carbazolederivatives (for example CBP, N,N-biscarbazolylbiphenyl) or compounds inaccordance with WO 2005/039246, US 2005/0069729, JP 2004/288381, EP1205527 or WO 2008/086851, bridged carbazole derivatives, for example inaccordance with WO 2011/088877 and WO 2011/128017, indenocarbazolederivatives, for example in accordance with WO 2010/136109 and WO2011/000455, azacarbazole derivatives, for example in accordance with EP1617710, EP 1617711, EP 1731584, JP 2005/347160, indolocarbazolederivatives, for example in accordance with WO 2007/063754 or WO2008/056746, ketones, for example in accordance with WO 2004/093207 orWO 2010/006680, phosphine oxides, sulfoxides and sulfones, for examplein accordance with WO 2005/003253, oligophenylenes, bipolar matrixmaterials, for example in accordance with WO 2007/137725, silanes, forexample in accordance with WO 2005/111172, azaboroles or boronic esters,for example in accordance with WO 2006/117052, triazine derivatives, forexample in accordance with WO 2010/015306, WO 2007/063754 or WO2008/056746, zinc complexes, for example in accordance with EP 652273 orWO 2009/062578, aluminium complexes, for example BAlq, diazasilole andtetraazasilole derivatives, for example in accordance with WO2010/054729, diazaphosphole derivatives, for example in accordance withWO 2010/054730, and aluminium complexes, for example BAlq.

Suitable charge-transport materials, as can be used in thehole-injection or hole-transport layer or in the electron-transportlayer of the organic electro-luminescent device according to theinvention, are, for example, the corn-pounds disclosed in Y. Shirota etal., Chem. Rev. 2007, 107(4), 953-1010, or other materials as areemployed in these layers in accordance with the prior art.

The cathode of the organic electroluminescent device preferablycomprises metals having a low work function, metal alloys ormultilayered structures comprising various metals, such as, for example,alkaline-earth metals, alkali metals, main-group metals or lanthanoids(for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable arealloys comprising an alkali metal or alkaline-earth metal and silver,for example an alloy comprising magnesium and silver. In the case ofmultilayered structures, further metals which have a relatively highwork function, such as, for example, Ag or Al, can also be used inaddition to the said metals, in which case combinations of the metals,such as, for example, Ca/Ag, Mg/Ag or Ag/Ag, are generally used. It mayalso be preferred to introduce a thin interlayer of a material having ahigh dielectric constant between a metallic cathode and the organicsemiconductor. Suitable for this purpose are, for example, alkali metalfluorides or alkaline-earth metal fluorides, but also the correspondingoxides or carbonates (for example LiF, Li₂O, BaF₂, MgO, NaF, CsF,Cs₂CO₃, etc.). Furthermore, lithium quinolinate (LiQ) can be used forthis purpose. The layer thickness of this layer is preferably between0.5 and 5 nm,

The anode preferably comprises materials having a high work function.The anode preferably has a work function of greater than 4.5 eV vs.vacuum. Suitable for this purpose are on the one hand metals having ahigh redox potential, such as, for example, Ag, Pt or Au. On the otherhand, metal/metal oxide electrodes (for example Al/Ni/NiO_(x),Al/PtO_(x)) may also be preferred. For some applications, at least oneof the electrodes must be transparent or partially transparent in orderto facilitate either irradiation of the organic material (organic solarcells) or the coupling-out of light (OLEDs, O-lasers). Preferred anodematerials here are conductive mixed metal oxides. Particular preferenceis given to indium tin oxide (ITO) or indium zinc oxide (IZO).

Preference is furthermore given to conductive, doped organic materials,in particular conductive, doped polymers.

The device is appropriately (depending on the application) structured,provided with contacts and finally sealed, since the lifetime of thedevices according to the invention is shortened in the presence of waterand/or air.

In a preferred embodiment, the organic electroluminescent deviceaccording to the invention is characterised in that one or more layersare coated by means of a sublimation process, in which the materials areapplied by vapour deposition in vacuum sublimation units at an initialpressure of less than 10⁻⁵ mbar, preferably less than 10⁻⁶ mbar.However, it is also possible here for the initial pressure to be evenlower, for example less than 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are coated by means of the OVPD(organic vapour phase deposition) process or with the aid of carrier-gassublimation, in which the materials are applied at a pressure of between10⁻⁵ mbar and 1 bar. A special case of this process is the OVJP (organicvapour jet printing) process, in which the materials are applieddirectly through a nozzle and are thus structured (for example M. S.Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting, nozzle printing or offset printing, but particularlypreferably LITI (light induced thermal imaging, thermal transferprinting) or ink-jet printing. Soluble compounds of the formula (1) arenecessary for this purpose. High solubility can be achieved throughsuitable substitution of the compounds.

For the production of an organic electroluminescent device according tothe invention, it is furthermore preferred to apply one or more layersfrom solution and one or more layers by a sublimation process.

In accordance with the invention, the electronic devices comprising oneor more compounds of the formula (1) or (167) can be employed indisplays, as light sources in lighting applications and as light sourcesin medical and/or cosmetic applications (for example light therapy).

Devices comprising the compounds of the formula (1) or (167) can beemployed in a very versatile manner. Thus, for example,electroluminescent devices comprising one or more compounds of theformula (1) or (167) can be employed in displays for televisions, mobiletelephones, computers and cameras. However, the devices can also be usedin lighting applications. Furthermore, electroluminescent devices, forexample in OLEDs or OLECs, comprising at least one of the compounds ofthe formula (1) or (167) can be used for phototherapy in medicine orcosmetics. Thus, a large number of diseases (psoriasis, atopicdermatitis, inflammation, acne, skin cancer, etc.) can be treated orskin wrinkling, skin reddening and skin ageing can be prevented orreduced. Furthermore, the light-emitting devices can be utilised inorder to keep drinks, meals or foods fresh or in order to steriliseequipment (for example medical equipment).

The compounds according to the invention and the organicelectroluminescent devices according to the invention are distinguishedby the following surprising advantages over the prior art:

-   -   1. The compounds according to the invention are very highly        suitable for use in a hole-transport layer or a hole-injection        layer in electronic devices, such as, for example, in organic        electroluminescent devices, in particular owing to their high        hole mobility.    -   2. The compounds according to the invention have a relatively        low sublimation temperature, high temperature stability and high        oxidation stability and a high glass-transition temperature,        which is advantageous both for the processability, for example        from solution or from the gas phase, and also for use in        electronic devices.    -   3. The use of the compounds according to the invention in        electronic devices, in particular employed as hole-transport or        hole-injection material, results in high efficiencies, low        operating voltages and long lifetimes.

It should be pointed out that variations of the embodiments described inthe present invention fall within the scope of this invention. Eachfeature disclosed in the present invention can, unless explicitlyexcluded, be replaced by alternative features which serve the same, anequivalent or a similar purpose. Thus, each feature disclosed in thepresent invention is, unless stated otherwise, to be regarded as anexample of a generic series or as an equivalent or similar feature.

All features of the present invention can be combined with one anotherin any way, unless certain features and/or steps are mutually exclusive.This applies in particular to preferred features of the presentinvention. Equally, features of non-essential combinations can be usedseparately (and not in combination).

It should furthermore be pointed out that many of the features, and inparticular those of the preferred embodiments of the present invention,are themselves inventive and should not merely be regarded as part ofthe embodiments of the present invention. For these features,independent protection may be sought in addition or as an alternative toeach invention currently claimed.

The teaching on technical action disclosed with the present inventioncan be abstracted and combined with other examples.

The invention is explained in greater detail by the following examples,without wishing to restrict it thereby.

EXAMPLES

Materials

Materials HIL1, HIL2 (EP 0676461), H1 (WO 2008/145239), ETM1 (WO2005/053055), SEB1 (WO 2008/006449), LiQ and NPB are well known to theperson skilled in the art. Their properties and syntheses are known fromthe prior art. Compounds (3-3), (3-1), (2-1) and (2-2) and (2-7) are inaccordance with the invention.

Example 1 Synthesis of the compoundbiphenyl-2-ylbiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (1-1) andCompounds (1-2) to (1-5)

23.5 g of biphenyl-2-ylbiphenyl-4-ylamine (73 mmol) and 20.0 g of2-bromofluorene (73 mmol) are dissolved in 500 ml of toluene: thesolution is degassed and saturated with N₂. 2.52 g (2.93 mmol) oftri-tert-butylphosphine and 0.33 g (1.46 mmol) of palladium(II) acetateare then added. 10.8 g of sodium tert-butoxide (110 mmol) aresubsequently added. The reaction mixture is heated at the boil for 6 hunder a protective atmosphere. The mixture is subsequently partitionedbetween toluene and water, and the organic phase is washed three timeswith water, dried over Na₂SO₄ and evaporated in a rotary evaporator.After the crude product has been filtered through silica gel withtoluene, the residue which remains is recrystallised fromheptane/toluene and finally sublimed in a high vacuum. The purity is99.9%. The yield is 32.0 g (85% of theory).

The following compounds (1-2) to (1-5) are prepared analogously:

Starting Starting material 1 material 2 Product Yield

78%

92%

88%

77%

Example 2 Synthesis of the Compoundbiphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (2-1) andCompounds (2-2) to (2-10)

2-Bromo-9,9-diphenyl-9H-fluorene (2-1)

30 g (103 mmol) of methyl 4′-bromobiphenyl-2-carboxylate are dissolvedin 500 ml of dried THF in a flask which has been dried by heating. Theclear solution is cooled to −10° C., and 102 ml (307 mmol) of a freshlyprepared 3 M 2-phenylmagnesium bromide solution are then added. Thereaction mixture is slowly warmed to room temperature and then quenchedusing NH₄Cl (500 ml).

The mixture is subsequently partitioned between ethyl acetate and water,and the organic phase is washed three times with water, dried overNa₂SO₄ and evaporated in a rotary evaporator. 400 ml of acetic acid arecarefully added to the residue. 80 ml of fuming HCl are subsequentlyadded. The batch is heated to 75° C. and kept at this temperature for 5h. A white solid precipitates out during this time. The batch is thencooled to room temperature, and the precipitated solid is filtered offwith suction and rinsed with methanol. The residue is dried at 40° C. invacuo. The yield is 29.4 g (74 mmol) (72% of theory).

The following brominated compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

65%

70%

72%

80%

Biphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (2-1)

17 g of biphenyl-2-ylbiphenyl-4-ylamine (53 mmol) and 21 g of2-bromo-9,9-diphenyl-9H-fluorene (53 mmol) are dissolved in 350 ml oftoluene: the solution is degassed and saturated with N₂. 2.1 ml (2.1mmol) of a 1 M solution of tri-tert-butylphosphine and 0.24 g (1.06mmol) of palladium(II) acetate are then added, and 12.7 g of sodiumtert-butoxide (132 mmol) are subsequently added. The reaction mixture isheated at the boil for 5 h under a protective atmosphere. The mixture issubsequently partitioned between toluene and water, and the organicphase is washed three times with water, dried over Na₂SO₄ and evaporatedin a rotary evaporator. After the crude product has been filteredthrough silica gel with toluene, the residue which remains isrecrystallised from heptane/toluene and finally sublimed in a highvacuum. The purity is 99.9%. The yield is 25 g (74% of theory).

The following compounds (2-2) to (2-10) can be prepared analogously.

Starting Starting material 1 material 2 Product Yield

72%

78%

81%

75%

75%

77%

65%

62%

70%

Example 3 Synthesis of the Compoundbiphenyl-4-ylbiphenyl-2-yl-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)amine(3-1) and Compounds (3-2) to (3-8)

9,9-Dimethyl-7-phenyl-9H-fluorene

8.9 g (73 mmol) of benzeneboronic acid and 20 g (73 mmol) of2-bromo-9,9′-dimethyl-9H-fluorene are suspended in 330 ml ofdimethoxyethane and 110 ml of 2 M Na₂CO₃ solution. 2.54 g (2.0 mmol) oftetrakis(triphenyl-phosphine)palladium are added to this suspension. Thereaction mixture is heated under reflux for 16 h. After cooling, thereaction mixture is diluted with ethyl acetate, and the organic phase isseparated off, washed three times with 100 ml of water and subsequentlyevaporated to dryness. Filtration of the crude product through silicagel with heptane/ethyl acetate (20:1) gives 18.8 g (95%) of9,9-dimethyl-7-phenyl-9H-fluorene.

The following fluorenes are prepared analogously.

Starting Starting material 1 material 2 Product Yield

90%

93%

88%

95%

80%

2-Bromo-9,9-dimethyl-7-phenyl-9H-fluorene

29.0 g (107 mmol) of 9,9-dimethyl-2-phenyl-9H-fluorene are dissolved in250 ml of CHCl₃, and 17.2 g (107 mmol) of bromine, dissolved in 50 ml ofCHCl₃, are slowly added at −10° C. When the reaction is complete, wateris added, and the organic phase is separated off, dried and evaporated.The crude product is subsequently washed a number of times by stirringwith hot MeOH/heptane (1:1). The yield is 33.3 g (89% of theory) of theproduct as a white solid.

The following brominated compounds are prepared analogously.

Starting material 1 Product Yield

80%

75%

72%

65%

80%

Biphenyl-4-ylbiphenyl-2-yl-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)amine(3-1)

19.9 g of biphenyl-2-ylbiphenyl-4-ylamine (62 mmol) and 21.6 g of2-bromo-9,9-dimethyl-7-phenyl-9H-fluorene (62 mmol) are dissolved in 400ml of toluene. The solution is degassed and saturated with N₂. 3 ml (3mmol) of a 1 M tri-tert-butylphosphine solution and 0.57 g (2 mmol) ofpalladium(II) acetate are then added. 14.9 g of sodium Cert-butoxide(155 mmol) are subsequently added. The reaction mixture is heated at theboil for 5 h under a protective atmosphere. The mixture is subsequentlypartitioned between toluene and water, and the organic phase is washedthree times with water, dried over Na₂SO₄ and evaporated in a rotaryevaporator. After the crude product has been filtered through silica gelwith toluene, the residue which remains is recrystallised fromheptane/toluene and finally sublimed in a high vacuum. The purity is99.9%. The yield is 29.7 g (82% of theory).

Compounds (3-2) to (3-8) are prepared analogously,

Starting Starting material 1 material 2 Product Yield

77%

87%

84%

75%

82%

85%

76%

Example 4 Synthesis of Comparative Compounds HTMV1 to HTMV6

The following comparative compounds (HTMV1) to (HTMV6) are also preparedanalogously to the synthesis of compound (3-1) described in Example 3.

Starting Starting material 1 material 2 Product

Example 5 Characterisation of the Compounds

OLEDs according to the invention and OLEDs in accordance with the priorart are produced by a general process in accordance with WO 04/058911,which is adapted to the circumstances described here (layer-thicknessvariation, materials).

The data for various OLEDs are presented in the following examples (seeTables 1, 3 and 2, 4). The substrates used are glass plates which havebeen coated with structured ITO (indium tin oxide) in a thickness of 50nm. The OLEDs basically have the following layer structure:substrate/optional hole-injection layer (HIL1)/hole-transport layer(HTL)/hole-injection layer (HIL2)/electron-blocking layer (EBL)/emissionlayer (EML)/electron-transport layer (ETL)/optional electron-injectionlayer (EIL) and finally a cathode. The cathode is formed by an aluminiumlayer with a thickness of 100 nm. The precise structure of the OLEDs isshown in Tables 1 and 3. The materials required for the production ofthe OLEDs are indicated above.

All materials are applied by thermal vapour deposition in a vacuumchamber. The emission layer here always consists of at least one matrixmaterial (host material) and an emitting dopant (emitter) with which thematrix material or matrix materials is (are) admixed in a certainproportion by volume by co-evaporation. An expression such as H1:SEB1(95%:5%) here means that material H1 is present in the layer in aproportion by volume of 95% and SEB1 is present in the layer in aproportion of 5%. Analogously, the electron-transport layer may alsoconsist of a mixture of two materials.

The OLEDs are characterised by standard methods. For this purpose, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in Im/W) and the external quantumefficiency (EQE, measured in per cent) as a function of the luminousdensity, calculated from current/voltage/luminous density characteristiclines (IUL characteristic lines) assuming Lambert emissioncharacteristics, and the lifetime are determined. Theelectroluminescence spectra are determined at a luminous density of 1000cd/m², and the CIE 1931 x and y colour coordinates are calculatedtherefrom. The expression EQE@1000 cd/m² denotes the external quantumefficiency at an operating luminous density of 1000 cd/m². LT80@6000cd/m² is the lifetime by which the OLED has dropped from a luminance of6000 cd/m² to 80% of the initial intensity, i.e. to 4800 cd/m². The datafor the various OLEDs are summarised in Tables 2 and 4.

Use of Compounds According to the Invention as Hole-Transport Materialsin Fluorescent and Phosphorescent OLEDs

The compounds according to the invention are particularly suitable asHIL, HTL or EBL in OLEDs. They are suitable as a single layer, but alsoas a mixed component as HIL, HTL, EBL or within the EML.

Compared with NPB reference components (V1, V8), the samples comprisingthe compounds according to the invention, besides higher efficiencies,also exhibit significantly improved lifetimes both for singlet blue andfor triplet green.

Compared with reference materials HTMV1-HTMV6 (V2-V10), the compoundsaccording to the invention have the same or better efficiencies andimproved lifetimes.

TABLE 1 Structure of the OLEDs Layer structure:substrate/HIL1/HTL/HIL2/EBL/EML/ETL/EIL 1 nm LiQ/cathode HIL1 HTL HIL2EBL EML ETL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nmThickness/nm Thickness/nm V1 HIL1 HIL2 HIL1 NPB H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V2 HIL1 HIL2 HIL1HTMV1 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm V3 HIL1 HIL2 HIL1 HTMV2 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm V4 HIL1 HIL2 HIL1 HTMV3 H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V5 HIL1 HIL2 HIL1HTMV4 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm V6 HIL1 HIL2 HIL1 HTMV5 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm V7 HIL1 HIL2 HIL1 HTMV6 H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E1 HIL1 HIL2 HIL1(3-3) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm E2 HIL1 HIL2 HIL1 (3-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm E3 HIL1 HIL2 HIL1 (2-1) H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E4 HIL1 HIL2 HIL1(2-2) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm E5 HIL1 HIL2 HIL1 (2-7) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm

TABLE 2 Data for the OLEDs EQE LT80 @ 1000 @ 6000 cd/m² cd/m² CIE Ex. %[h] x y V1 4.8 70 0.14 0.17 V2 6.9 120 0.13 0.14 V3 7.0 115 0.13 0.15 V46.8 105 0.13 0.15 V5 6.6 105 0.13 0.15 V6 6.6 120 0.13 0.14 V7 7.3 150.14 0.15 E1 7.2 140 0.13 0.15 E2 7.0 135 0.13 0.14 E3 6.6 150 0.13 0.15E4 6.4 145 0.13 0.15 E5 6.6 155 0.13 0.15

TABLE 3 Structure of the OLEDs Layer structure:substrate/HTL/HIL2/EBL/EML/ETL/cathode HTL HIL2 EBL EML ETL Thickness/Thickness/ Thickness/ Thickness/ Thickness/ Ex nm nm nm nm nm V8 HIL2HIL1 NPB H2(88%): Irpy(12%) ETM1(50%): LiQ(50%) 70 nm 5 nm 20 nm 30 nm40 nm V9 HIL2 HIL1 HTMV5 H2(88%): Irpy(12%) ETM1(50%): LiQ(50%) 70 nm 5nm 20 nm 30 nm 40 nm V10 HIL2 HIL1 HTMV6 H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E6 HIL2 HIL1 (2-1) H2(88%):Irpy(12%) ETM1(50%): LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E7 HIL2 HIL1(2-2) H2(88%): Irpy(12%) ETM1(50%): LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40nm E8 HIL2 HIL1 (2-7) H2(88%): Irpy(12%) ETM1(50%): LiQ(50%) 70 nm 5 nm20 nm 30 nm 40 nm

TABLE 4 Data for the OLEDs Efficiency LT80 @ 1000 @ 8000 cd/m² cd/m² CIEEx. % [h] x y V8 13.4 85 0.32 0.63 V9 17.0 155 0.37 0.61 V10 18.1 650.37 0.61 E6 17.6 195 0.37 0.61 E7 17.1 185 0.37 0.61 E8 17.5 200 0.370.61

1.-21. (canceled)
 22. An electroluminescent device comprising at leastone compound of the general formula (1)

where the following applies to the symbols and indices occurring: Ar¹and Ar² are on each occurrence, identically or differently, an aromaticor heteroaromatic group having two or more aromatic or heteroaromaticrings and having 10 to 60 ring atoms in said aromatic or heteroaromaticgroup, which is optionally substituted by one or more radicals R⁴, whichare identical to or different from one another, wherein either Ar¹ orAr² comprises at least one heteroaromatic group having 6 to 60 aromaticring atoms, which is optionally substituted by one or more radicals R⁴,which are identical to or different from one another; R¹ is on eachoccurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R⁵, CN,Si(R⁵)₃, NO₂, P(═O)(R⁵)₂, S(═O)R⁵, S(═O)₂R⁵, a straight-chain alkyl,alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclicalkyl. alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl oralkynyl group having 2 to 20 C atoms, where the above-mentioned groupsmay each be substituted by one or more radicals R⁵ and where one or moreCH₂ groups in the above-mentioned groups is optionally replaced by—R⁵C═CR⁵—, —C≡C—, Si(R⁵)₂, C═O, C═S, C═NR⁵, —C(═O)O—, —C(═O)NR⁵—,P(═O)(R⁵), —O—, —S—, SO or SO₂ and where one or more H atoms in theabove-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN orNO₂, or an aromatic or heteroaromatic ring system having 6 to 30 ringatoms, which may in each case be substituted by one or more radicals R⁵,or a condensed ring system having 9 to 30 ring atoms, which may in eachcase be substituted by one or more radicals R⁵, where, in the case ofaromatic or heteroaromatic condensed rings, not more than 10 ring atomsis optionally present; the two radicals R¹ may also form a ring closurewith one another, so that a spiro compound forms, where no aromatic orheteroaromatic rings are condensed onto the ring formed by the tworadicals R¹; R², R³ and R⁴ are on each occurrence, identically ordifferently, H, D, F, Cl, Br, I, C(═O)R⁵, CN, Si(R⁵)₃, NO₂, P(═O)(R⁵)₂,S(═O)R⁵, S(═O)₂R⁵, a straight-chain alkyl, alkoxy or thioalkyl grouphaving 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy orthioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl grouphaving 2 to 20 C atoms, where the above-mentioned groups may each besubstituted by one or more radicals R⁵ and where one or more CH₂ groupsin the above-mentioned groups is optionally replaced by —R⁵C═CR⁵—,—C≡C—, Si(R⁵)₂, C═O, C═S, C═NR⁵, —C(═O)O—, —C(═O)NR⁵—, P(═O)(R⁵),—O—,—S—, SO or SO₂ and where one or more H atoms in the above-mentionedgroups is optionally replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 6 to 30 ring atoms, whichmay in each case be substituted by one or more radicals R⁵; R⁵ is oneach occurrence, identically or differently, H, D, F, Ci, Br, I,C(═O)R⁶, CN, Si(R⁶)₃, NO₂, P(═O)(R⁶)₂, S(═O)R⁶, S(═O)₂R⁶, astraight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atomsor a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR⁶ and where one or more CH₂ groups in the above-mentioned groups isoptionally replaced by —R⁶C═CR⁶—, —C≡C—, Si(R⁶)₂, C═O, C═S, C═NR⁶,—C(═O)O—, —C(═O)NR⁶—, P(═O)(R⁶), —O—, —S—, SO or SO₂ and where one ormore H atoms in the above-mentioned groups is optionally replaced by D,F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemhaving 5 to 30 aromatic ring atoms, which may in each case besubstituted by one or more radicals R⁶, or an aryloxy or heteroaryloxygroup having 5 to 30 aromatic ring atoms, which is optionallysubstituted by one or more radicals R⁶; R⁶ is on each occurrence,identically or differently, H, D, F or an aliphatic, aromatic orheteroaromatic organic radical having 1 to 20 C atoms, in which, inaddition, one or more H atoms is optionally replaced by D or F; n is 0,1, 2, 3 or 4; m is 0, 1, 2 or 3; with the proviso that the compound ofthe formula (1), besides the one fluorene group and besides the possiblecondensed or polycyclic groups in position 9 of the fluorene, containsno further polycyclic or condensed groups.
 23. The device according toclaim 22, wherein the two radicals R¹ in the compound of the formula (1)are identical.
 24. The device according to claim 22, wherein m is equalto 1 and n is equal to 0, 1 or
 2. 22. e device according to claim 22,wherein it comprises at least one compound of the general formula (2)

where the definitions from claim 22 apply to the symbols.
 26. The deviceaccording to claim 22, wherein R³ is equal to H.
 27. The deviceaccording to claim 22, wherein Ar¹ and Ar² are identical or differentand are selected from a biphenyl, terphenyl or quaterphenyl group, eachof which is optionally substituted by one or more radicals R⁴.
 28. Thedevice according to claim 22, wherein the two radicals R¹ are identicaland are selected from an aromatic or heteroaromatic ring system having 6to 30 ring atoms, which may in each case be substituted by one or moreradicals R⁵, or a condensed ring system having 9 to 30 ring atoms, whichmay in each case be substituted by one or more radicals R⁵, where, inthe case of aromatic or heteroaromatic condensed rings, not more than 10ring atoms is optionally present and where R² is equal to H.
 29. Thedevice according to claim 22, wherein the two radicals R² are identicaland are selected from a straight-chain alkyl group having 1 to 20 Catoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherethe groups may each be substituted by one or more radicals R⁵ and whereone or more H atoms in the above-mentioned groups is optionally replacedby D, F, Cl, Br, I, CN or NO₂ and where R² is an aromatic orheteroaromatic ring system having 6 to 30 aromatic ring atoms, which mayin each case be substituted by one or more radicals R⁵.
 30. The deviceaccording to claim 22, wherein it is an organic light-emittingtransistor (OLET), an organic field-quench device (OFQD), an organiclight-emitting electrochemical cell (OLEC, LEC or LEEC), an organiclaser diode (O-laser) or an organic light-emitting diode (OLED).
 31. Thedevice according to claim 22, wherein the device is an organiclight-emitting diode (OLED), wherien the compound is employed in one ofthe following functions: as hole-transport material in a hole-transportor hole-injection layer, as matrix material in an emitting layer, aselectron-blocking material or as exciton-blocking material.
 32. Acompound of the general formula (167)

where the following applies to the symbols used in formula (167): Ar³and Ar⁴ are on each occurrence, identically or differently, an aromaticor heteroaromatic group having two or more aromatic or heteroaromaticrings and having 10 to 60 ring atoms in said aromatic or h.eteroaromaticgroup, which is optionally substituted by one or more radicals R⁵, whichare identical to or different from one another, wherein either Ar³ orAr⁴ comprises at least one heteroaromatic group having 6 to 60 aromaticring atoms, which is optionally substituted by one or more radicals R⁵,which are identical to or different from one another; R⁷ is identical oneach occurrence and is selected from the group consisting of astraight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atomsor a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR⁵ and where one or more H atoms in the above-mentioned groups isoptionally replaced by D, CN or NO₂, or an aromatic or heteroaromaticring system having 6 to 30 ring atoms, which may in each case besubstituted by one or more radicals R⁵, where R⁵ is defined as indicatedabove, or a condensed ring system having 9 to 30 ring atoms, which mayin each case be substituted by one or more radicals R⁵, where, in thecase of aromatic or heteroaromatic condensed rings, not more than 10ring atoms is optionally present in the condensed ring system; the tworadicals R⁷ may also form a ring closure with one another, so that aSpiro compound forms, where no aromatic or heteroaromatic rings arecondensed onto the ring formed by the two radicals R⁷, and where, if R⁷is a straight-chain or branched alkyl group, R⁸ is an aromatic orheteroaromatic ring system having 6 to 30 ring atoms, which may in eachcase be substituted by one or more radicals .⁵, and where R⁵ is definedas indicated above; R⁸ is H, D or an aromatic or heteroaromatic ringsystem having 6 to 30 ring atoms, which may in each case be substitutedby one or more radicals R⁵, where R⁵ is defined as indicated above andwhere, if R⁸ is equal to H, R⁷ is an aromatic or heteroaromatic ringsystem having 6 to 30 aromatic ring atoms, which may in each case besubstituted by one or more radicals R⁵, where R⁵ is defined as indicatedabove; a is either 1, 2, 3 or 4; with the proviso that the compound ofthe formula (167), besides the one fluorene group and besides thepossible condensed or polycyclic groups in position 9 of the fluorene,contains no further polycyclic or condensed groups and with the provisothat the compound contains no halogens.
 33. The compound according toclaim 32, wherein the compound has the general formula (168)

where, for the symbols used, Ar¹ and Ar⁴ are identical or different oneach occurrence and are selected from a biphenyl, terphenyl orquaterphenyl group, which is optionally substituted by one or moreradicals R⁵; R⁷ is identical on each occurrence and is selected from anaromatic or heteroaromatic ring system having 6 to 30 ring atoms, whichmay in each case be substituted by one or more radicals R⁵, where R⁵ isdefined as indicated above, or a condensed ring system having 9 to 30ring atoms, which may in each case be substituted by one or moreradicals R⁵, where, in the case of aromatic or heteroaromatic condensedrings, not more than 10 ring atoms is optionally present in thecondensed ring system.
 34. The compound according to claim 32, whereinthe compound has the general formula (169)

where, for the symbols used, X is, identically or differently on eachoccurrence, N or CR⁵, preferably X is equal to CR⁵; Ar³ and Ar⁴ areidentical or different on each occurrence and are selected from abiphenyl, terphenyl and quaterphenyl group, each of which is optionallysubstituted by one or more radicals R⁵; and R⁵ is on each occurrence,identically or differently, H, D, F, Cl, Br, I, C(═O)R⁶, CN, Si(R⁶)₃,NO₂, P(═O)(R⁶)₂, S(═O)R⁶, S(═O)₂R⁶, a straight-chain alkyl, alkoxy orthioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl,alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl oralkynyl group having 2 to 20 C atoms, where the above-mentioned groupsmay each be substituted by one or more radicals R⁶ and where one or moreCH₂ groups in the above-mentioned groups is optionally replaced by—R⁶C═CR⁶—, Si(R⁶)₂, C═O, C═S, C═NR⁶, —C(═O)O—, —C(═O)NR⁶—, P(═O)(R⁶),—O—, —S—, SO or SO₂ and where one or more H atoms in the above-mentionedgroups is optionally replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 5 to 30 aromatic ringatoms, which may in each case be substituted by one or more radicals R⁶,or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms,which is optionally substituted by one or more radicals R⁶; R⁶ is oneach occurrence, identically or differently, H, D, F or an aliphatic,aromatic or heteroaromatic organic radical having 1 to 20 C atoms, inwhich, in addition, one or more H atoms is optionally replaced by D orF.
 35. A process for the preparation of the compound according to claim32 by means of one-step Buchwald coupling by reacting a fluorenederivative containing a leaving group with Ar³-Ar⁴.
 36. A process forthe preparation of the compound according to claim 32 by means oftwo-step Buchwald coupling by stepwise reacting a phenanthrenederivative containing a leaving group with (1) Ar³-NH₂ and (2) NH₂-Ar⁴.37. An oligomer, polymer or dendrimer containing one or more compoundsaccording to claim 32, where the bond(s) to the polymer, oligomer ordendrimer is optionally localised at any positions.
 38. A compositioncomprising one or more compounds according to claim 32 and at least onefurther organically functional material selected from the groupconsisting of fluorescent emitters, phosphorescent emitters, hostmaterials, matrix materials, electron-transport materials,electron-injection materials, hole-conductor materials, hole-injectionmaterials, electron-blocking materials and hole-blocking materials. 39.A formulation comprising at least one compound according to claim 32 andat least one solvent.
 40. An electronic device comprising at least onecompound according to claim
 32. 41. The electronic device according toclaim 40, wherein the device is selected from the group consisting oforganic integrated circuits (O-ICs), organic field-effect transistors(O-FETs), organic thin-film transistors (O-TFTs), organic light-emittingtransistors (O-LETs), organic solar cells (O-SCs), organic opticaldetectors, organic photoreceptors, organic field-quench devices(O-FQDs), light-emitting electrochemical cells (LECs), organic laserdiodes (O-lasers) and organic electroluminescent devices (OLEDs).
 42. Anorganic electroluminescent device which comprises the compound accordingto claim 32 is employed in one or more of the following functions: ashole-transport material in a hole-transport or hole-injection layer, asmatrix material in an emitting layer, as electron-blocking material oras exciton-blocking material.
 43. The device according to claim 22,wherein at least one Ar¹ or Ar² are selected from the group consistingof radicals having the formulae (43)-(55), (94)-(96), (138)-(140) and(201)-(203):